TW201831934A - Method for manufacturing GI-type optical waveguide - Google Patents

Abstract

To provide a GI optical waveguide comprising a core having a substantially circular cross-sectional shape. A method for manufacturing an optical waveguide, including: a first step for inserting a needle-shaped part on a distal end of a discharging part into an uncured cladding part; a second step for moving the needle-shaped part within the uncured cladding part while discharging uncured material from the needle-shaped part to form an uncured core part enveloped by the uncured cladding part; a third step for withdrawing the needle-shaped part from the uncured cladding part; and a fourth step for curing the uncured cladding part and the uncured core part; wherein said method is characterized in that the ratio of the viscosity of the material forming the uncured core part to the viscosity of the uncured cladding part at the temperature of the second step is 1.20 to 6.

Description

ＧＩ型光波導之製造方法Manufacturing method of GI optical waveguide

[0001] 本發明係有關GI型光波導之製造方法，詳細地說係有關核心的剖面形狀為略圓形之GI型光波導之製造方法。[0001] The present invention relates to a method for manufacturing a GI-type optical waveguide, and in particular, to a method for manufacturing a GI-type optical waveguide in which the cross-sectional shape of the core is slightly circular.

[0002] 近年，藉由大數據的發展或智慧型手機使用者的增加，通信流量係日趨增加。因此，在所送訊之資訊資料所集中之資料伺服器，產生巨大的電力使用量，更且接近處理量的極限之問題則表面化，而為了改善此等之技術進展則成為當務之急。其中，作為可高密度且高速地處理資訊的技術，大力地檢討有將伺服器板內之一部分的電性配線變更為光配線之光電混載基板(亦稱為光電複合基板)之技術。 　　在光電混載基板中，由面發光雷射(VCSEL)或矽光子所代表之將電性信號變換為光信號之光電變換元件，與光傳送路徑之光波導則成為必要。 　　[0003] 此外，光波導係從其構造，大致分為階梯式折射率型(SI型)與漸變式折射率型(GI型)之兩種構造。以往的光波導係從其加工性的觀點，利用SI型。SI型係在核心部與覆蓋部形成明確的折射率之界面，藉由其界面反射而使光傳導。另一方面，GI型係具有核心中心則折射率為最高，而伴隨著朝向外側而折射率逐漸地減少之構造，藉由此，僅對於核心中心附近誘導光線而傳導。因此，GI型係即使將核心彼此作為窄間距化，亦未產生干擾，另外，理論上，具有未產生藉由界面反射所致之傳導損失之特性，而在高密度且長距離的光波導為必要之光電混載基板中，作為理想之光波導形狀。 　　[0004] 但，GI型光波導係製造難易度為高而報告例有限。作為數量少之GI型光波導之製造方法係知道有：由光照射於特定之降莰烯樹脂與環氧化合物者，誘發光分解物及光硬化性之環氧化合物的物質擴散，使折射梯度產生的手法(專利文獻1)。另外，作為簡便且泛用之手法係報告有：於成為覆蓋之光硬化性樹脂之中，以分配器而配線描繪成為核心之光硬化性樹脂的注入法，所謂Mosquito法(專利文獻2)。 [先前技術文獻] [專利文獻] 　　[0005] 　　[專利文獻1] 日本特開2012-198488號公報 　　[專利文獻2] 國際公開第2013/002013號小冊子[0002] In recent years, with the development of big data or the increase of smart phone users, communication traffic has been increasing. Therefore, the problem of generating a huge amount of power in the data server where the information and information to be transmitted is closer to the limit of the processing amount is apparent, and it is imperative to improve such technological progress. Among them, as a technology capable of processing information at a high density and at a high speed, there has been vigorously reviewed a technology of changing an electrical wiring in a server board to an optical hybrid substrate (also referred to as a photoelectric composite substrate) of optical wiring. In the photoelectric hybrid substrate, a photoelectric conversion element represented by a surface emitting laser (VCSEL) or a silicon photon that converts an electrical signal into an optical signal, and an optical waveguide of an optical transmission path becomes necessary. [0003] In addition, the optical waveguide system is roughly divided into two types of structures: a stepped refractive index type (SI type) and a graded refractive index type (GI type) from its structure. The conventional optical waveguide system uses an SI type from the viewpoint of workability. The SI type system forms a clear refractive index interface between the core portion and the cover portion, and transmits light through the interface reflection. On the other hand, the GI type system has a structure in which the refractive index is the highest at the core center, and gradually decreases as the refractive index is directed outward. As a result, light is induced and transmitted only near the core center. Therefore, the GI type system does not cause interference even if the cores are narrowed to each other. In addition, in theory, it has the characteristic of not causing conduction loss due to interface reflection. In a high-density and long-distance optical waveguide, It is an ideal optical waveguide shape in the necessary optoelectronic hybrid substrate. [0004] However, the GI type optical waveguide system has a high degree of difficulty in manufacturing and has limited reporting examples. As a method for manufacturing a small number of GI-type optical waveguides, it is known that those who irradiate a specific norbornene resin and an epoxy compound with light induce diffusion of a photodegradable substance and a photo-hardenable epoxy compound, thereby causing a refractive gradient. Production method (Patent Document 1). In addition, as a simple and widely used method system, there is a so-called Mosquito method (patent document 2), which is an injection method in which a light-curing resin is drawn by using a dispenser as a core among the light-curing resins to be covered. [Prior Art Document] [Patent Document] [0005] [Patent Document 1] Japanese Patent Application Publication No. 2012-198488 88 [Patent Document 2] International Publication No. 2013/002013

[發明欲解決之課題] 　　[0006] 上述Mosquito法係為非常簡便且泛用的手法，但為了注入成為核心之光硬化性樹脂於未硬化之覆蓋內，核心的剖面形狀之控制則為困難，而有其剖面形狀成為形變者之虞。另外，形變之光波導係藉由在該光波導的出射界面，核心的剖面形狀則自圓形變形，光強度分布則擴散於出射界面全體，而光無法封閉於核心中心附近，結果上，作為光波導之***損失則惡化。因此，要求其剖面形狀為略圓形而***損失的惡化為少之GI型光波導之製造方法。 [為了解決課題之手段] 　　[0007] 本發明者們係為了達成上述目的而重複致力檢討的結果，發現藉由將成為核心的光硬化性樹脂與成為覆蓋之光硬化性樹脂之黏度比作為特定的範圍之時，可形成核心的剖面形狀為略圓形之GI型光波導，而完成本發明。 　　[0008] 即，本發明作為第1觀點係關於一種光波導之製造方法具有刺入吐出部前端的針狀部於未硬化之覆蓋部的第1工程，和自前述針狀部吐出未硬化之材料的同時，使前述針狀部移動在前述未硬化之覆蓋部內，形成使前述未硬化之覆蓋部被覆周圍之未硬化的核心部之第2工程，和自前述未硬化之覆蓋部拔去前述針狀部之第3工程，和使前述未硬化之覆蓋部及前述未硬化之核心部硬化的第4工程之光波導之製造方法，其特徵為在前述第2工程的溫度中，對於前述未硬化之覆蓋部的黏度而言，形成前述未硬化的核心部之材料的黏度比則為1.20~6者。 　　作為第2觀點係關於記載於第1觀點之製造方法，其中，有關於前述第3工程與前述第4工程之間，作為一連串的工程而重複實施前述第1工程，前述第2工程及前述第3工程，形成使前述未硬化之覆蓋部被覆周圍之複數的未硬化之核心部。 　　作為第3觀點係關於記載於第1觀點或第2觀點的製造方法，其中，有關前述光波導為在其剖面的核心部之折射率，則將核心部的中心作為最大值而朝向外周部，折射率則連續性地降低之光波導。 [發明效果] 　　[0009] 本發明之光波導之製造方法係可製造核心的剖面形狀為略圓形之GI型光波導，藉由此，成為可製造可抑制***損失之惡化的GI型光波導者。[Problems to be Solved by the Invention] 0006 [0006] The above-mentioned Mosquito method is a very simple and versatile method, but in order to inject the light-curing resin that becomes the core into the uncured cover, it is difficult to control the cross-sectional shape of the core. There is a risk that the cross-sectional shape will become deformed. In addition, in the deformed optical waveguide, the cross-sectional shape of the core is deformed from a circle at the exit interface of the optical waveguide, and the light intensity distribution is diffused throughout the exit interface, but the light cannot be enclosed near the core center. As a result, as The insertion loss of the optical waveguide deteriorates. Therefore, a manufacturing method of a GI type optical waveguide whose cross-sectional shape is slightly circular and which has less deterioration in insertion loss is required. [Means to Solve the Problem] [0007] As a result of repeated efforts to achieve the above-mentioned object, the present inventors have found that the specificity of the viscosity ratio of the photocurable resin as the core and the photocurable resin as the coating is specified. In the range of the above, a GI-type optical waveguide having a core with a slightly circular cross-sectional shape can be formed, and the present invention has been completed. [0008] That is, as a first aspect, the present invention relates to a first process for manufacturing a method of optical waveguides, which includes a first step of piercing a needle-shaped portion at a tip end of a discharge portion into an unhardened covering portion, and discharging the unhardened portion from the needle-shaped portion. At the same time as the material, the second process of moving the needle-shaped portion in the uncured covering portion to form an uncured core portion surrounding the uncured covering portion and removing the aforementioned from the uncured covering portion The third process of the acicular portion, and the method of manufacturing the optical waveguide of the fourth process of hardening the uncured covering portion and the uncured core portion are characterized in that at the temperature of the second process, In terms of the viscosity of the hardened cover, the viscosity ratio of the material forming the unhardened core is 1.20-6. The second viewpoint relates to the manufacturing method described in the first viewpoint, in which the first process, the second process, and the first process are repeatedly performed as a series of processes between the third process and the fourth process. 3 processes to form a plurality of unhardened core portions that cover the surroundings of the unhardened covering portion. As a third aspect, the manufacturing method described in the first aspect or the second aspect, wherein the optical waveguide has a refractive index at a core portion of a cross section thereof, the center of the core portion is directed toward the outer peripheral portion as a maximum value, An optical waveguide having a continuously reduced refractive index. [Effects of the Invention] [0009] The manufacturing method of the optical waveguide of the present invention is capable of manufacturing a GI-type optical waveguide having a cross-section of a core having a slightly circular cross-section, thereby making it possible to manufacture a GI-type optical waveguide capable of suppressing deterioration of insertion loss. By.

[0011] ＜光波導之製造方法＞ 　　本發明之光波導之製造方法係具有：刺入吐出部前端的針狀部於未硬化之覆蓋部的第1工程，和自前述針狀部吐出未硬化之材料的同時，使前述針狀部移動在前述未硬化之覆蓋部內，形成使前述未硬化之覆蓋部被覆周圍之未硬化的核心部之第2工程，和自前述未硬化之覆蓋部拔去前述針狀部之第3工程，和使前述未硬化之覆蓋部及前述未硬化之核心部硬化的第4工程。 　　另外，在本發明之製造方法中，在於前述第3工程與前述第4工程之間，作為一連串的工程而重複實施前述第1工程，前述第2工程及前述第3工程，形成使前述未硬化之覆蓋部被覆周圍之複數的未硬化之核心部之後，實施使未硬化之覆蓋部及前述未硬化之核心部硬化之第4工程亦可。 　　[0012] 在本發明之光波導之製造方法中，如後述，其特徵為前述第2工程的溫度中，對於前述未硬化之覆蓋部的黏度而言，形成前述未硬化的核心部之材料的黏度比則為1.20~6者。尚且，第2工程係通常，可以室溫而實施，隨之，前述未硬化的覆蓋部及核心部的黏度係稱為例如25℃±5℃之黏度。理想係該黏度比為1.5~6、而更理想為1.5~4。 　　藉由將該黏度比作為1.20~6之範圍，成為可形成核心的剖面形狀為略圓形之GI型光波導，進而係連結於抑制***損失之惡化的GI型光波導之製造。 　　尚且，在本發明中，「略圓形」係指：自核心的剖面形狀的最大寬度(水平方向)及最大高度(垂直方向)所算出之縱橫比(對於最大寬度及最大高度之任一為大之值而言之另一方的值的比，即以正圓來說成為最大值1)則為0.8以上之形狀。特別是，縱橫比如為0.9以上，成為可更抑制***損失之惡化的光波導而為佳。 　　[0013] 以下，對於製造本發明之光波導之實際一連串的步驟，詳述其一例。 　　圖1~圖6係例示光波導之製造工程的一部分的圖，有著將此製造工程稱為注入法之情況。 　　[0014] 首先，在圖1所示之工程中，準備支持體91。支持體91係於平面形狀為略矩形狀的底板92之周緣部，以可拆裝具有平面形狀成為略框緣狀之開口部93a的外框93之狀態而配設之構件。作為各底板92及外框93之材料係例如，可使用樹脂(丙烯酸等)，玻璃，矽，陶瓷，金屬等。但底板92與外框93係未使用同一材料亦可。底板92之上面係平坦性為高者為佳。 　　[0015] 接著，在圖2所示之工程中，於露出於支持體91之外框93內的底板92之上面，塗佈特定的材料，同樣地擴展而製作略一定層厚之未硬化的覆蓋部19A。 　　未硬化的覆蓋部19A係使用例如塗佈裝置(分配器等)或印刷裝置等而塗佈後述之覆蓋形成材料，或者，可藉由自開口部93a而充填(注入)製作。另外，在未硬化的覆蓋部19A之材料(覆蓋形成材料)中，使例如碳黑等的吸收光之素材含有亦可。 　　未硬化的覆蓋部19A之黏度係無特別限定，呈對於該黏度而言之後述的未硬化之核心部的黏度比則成為1.20~6地調整黏度即可。 　　另外，未硬化的覆蓋部19A之厚度係可藉由後述之核心部11~14之直徑或製造條件等而任意地決定，但理想係作為數mm左右，更理想為作為50~1,000μm左右者。 　　[0016] 接著，在圖3所示之工程中，準備具有吐出部94(具有吐出部主體95及針狀部96)之塗佈裝置(未圖示)，使所準備之塗佈裝置(未圖示)動作，將吐出部94前端的針狀部96之一部分，刺入至未硬化的覆蓋部19A(第1工程)。自支持體91之底板92的上面至針狀部96之前端部為止之高度H₁ 係可作適宜選擇，但例如可作為100~1,000μm左右者(未硬化的覆蓋部19A之層厚為數mm左右之情況)。 　　[0017] 尚且，塗佈裝置(未圖示)係含有CPU或記憶體等，藉由編組程式之時，具有使吐出部94對於未硬化的覆蓋部19A而言，以特定的移動速度，精度佳地移動於X方向、Y方向、及Z方向之機能。另外，針狀部96係例如，剖面形狀為圓環狀，而塗佈裝置(未圖示)係具有自針狀部96之圓環內，以特定的吐出壓力而使特定之材料吐出的機能。針狀部96之圓環的內徑係可作適宜選擇，但例如，可作為100~200μm左右者。另外，針狀部96之剖面形狀係除了圓環狀，亦可為方形狀。塗佈裝置(未圖示)係例如，可包含桌上型塗佈機器手臂或分配器等而構成者。 　　[0018] 接著，在圖4所示之工程中，使塗佈裝置(未圖示)作動，自刺入至未硬化的覆蓋部19A之針狀部96，作為形成未硬化的核心部之材料而吐出後述之核心形成材料的同時，使針狀部96移動於未硬化的覆蓋部19A內，形成未硬化的核心部11A(第2工程)。 　　尚且，在圖4中，(A)係平面圖，(B)係沿著(A)之C-C線的剖面圖。但在(A)中，吐出部94之圖示係被省略。針狀部96之移動方向係可作適宜選擇，但在此係作為一例僅於X方向移動。針狀部96之移動速度係可作適宜選擇，但例如，可作為5~30mm/s左右。針狀部96之吐出壓力係可作適宜選擇，但例如，可作為10~1,000kPa左右。 　　另外，未硬化的核心部11A之黏度係對於前述之未硬化的覆蓋部19A之黏度而言的比則如呈成為1.20~6地進行選擇即可。 　　[0019] 藉由將吐出部94之移動速度或針狀部96之吐出壓力，針狀部96之圓環的內徑，分別配合於形成未硬化的核心部11A之材料(核心形成材料)或形成未硬化的覆蓋部19A之材料(覆蓋形成材料)的性狀(黏度等)而進行調整之時，可連結於將未硬化核心部A之剖面形狀作為更接近於正圓形之略圓形者，並且在後述之硬化後，可形成越中心部折射率越高而越接近周邊部折射率越低之核心部11。未硬化的核心部11A之剖面形狀為略圓形之情況的直徑係例如，可作為5~200μm左右。 　　另外，使核心形成材料吐出之同時，藉由程式等而使吐出部94之移動速度或針狀部96之吐出壓力變化者，藉此亦可形成部分口徑不同之核心部11(點尺寸變換)。 　　[0020] 尚且，藉由將吐出部94之移動速度或針狀部96之吐出壓力，配合於未硬化的核心部11A之材料(核心形成材料)或未硬化的覆蓋部19A之材料(覆蓋形成材料)的性狀(黏度等)而進行調整之時，亦可製作較針狀部96之圓環的內徑為小徑之略圓形(剖面形狀)之未硬化的核心部11A者。 　　此係藉由調整各材料的黏度，而自針狀部96吐出更具黏性之未硬化的核心部11A的材料，針狀部之圓環的內側面與材料的摩擦力則變大，藉由此，以自圓環的內側面附近係不易吐出前述材料，僅與圓環的內側面未產生摩擦之圓環之中心部附近的前述材料優先地吐出而實現。 　　尚且，圖4的工程係通常可以室溫而實施，但可藉由冷卻板等之調溫裝置(未圖示)而調節溫度者。特別是於製作10μm以下之細口徑的核心部11A之情況，例如，作為10~20℃者為佳。 　　[0021] 在圖4所示之工程中，顯示固定形成有未硬化的覆蓋部19A之支持體91，使針狀部96移動在未硬化的覆蓋部19A內而形成未硬化的核心部11A的例。但未限定於如此之形態，而例如，固定針狀部96，使形成有未硬化的覆蓋部19A之支持體91移動而形成未硬化的核心部11A亦可。 　　[0022] 接著，在圖5所示之工程中，自圖4所示之狀態，使吐出部94移動於Z方向，自未硬化的覆蓋部19A拔去針狀部96(第3工程)。 　　尚且，之後，反覆進行圖3工程之針狀部96之對於未硬化的覆蓋部19A的刺入，和形成圖4之未硬化的核心部11A的工程，和圖5工程之自未硬化的覆蓋部19A的針狀部96之拔去，如圖6所示，呈並設於未硬化的核心部11A地形成未硬化之核心部12A，13A，及14A亦可。對於未硬化之核心部12A，13A，及14A之材料係使用與未硬化的核心部11A同種類之核心形成材料亦可，併用不同種類之核心形成材料亦可。另外，形成複數之核心部的情況，鄰接之核心部的間距係例如，可作為20~300μm左右者。 　　如前述，未硬化的覆蓋部19A係具有適度之流動性(黏度)之故，即使自未硬化的覆蓋部19A拔去針狀部96，拔去的痕跡係亦未殘留，另外，在形成未硬化之核心部11A，又12A、13A、及14A後，於與未硬化的覆蓋部19A之間未形成有界面。 　　尚且，在圖5及圖6中，(A)係平面圖，(B)係沿著(A)之C-C線(圖5)或D-D線(圖6)之剖面圖。但在各圖之(A)中，吐出部94之圖示係被省略。 　　[0023] 圖5及圖6所示之工程之後(未圖示)，將未硬化之核心部11A，又12A、13A、及14A，以及未硬化的覆蓋部19A，進行後述之特定方法，即，照射光(紫外線等)而使其硬化，或者進行加熱處理而使其硬化(第4工程)。於使用僅由光的照射而未完全地硬化之材料的情況，在照射光之後，更進行加熱亦可。 　　[0024] 上述光硬化之情況，作為使用於光照射之活性光線係例如，可舉出紫外線，電子線，X線等。作為使用於紫外線照射的光源，係可使用太陽光線，化學燈，低壓水銀燈，高壓水銀燈，鹵化金屬燈，氙氣燈，UV-LED等。另外，在光照射後，藉由因應必要而進行後烘焙之時，具體而言係使用加熱板，烘箱等，通常，可藉由以50~300℃進行1~120分鐘加熱而使硬化(聚合)完結者。 　　上述熱硬化之情況，作為其加熱條件係無特別限定，通常，可自50~300℃、1~120分鐘的範圍適宜選擇。另外，作為加熱手段係無特別限定，但例如，可舉出加熱板，烘箱等。 　　[0025] 藉由此硬化工程，未硬化之核心部11A，又12A、13A、及14A，以及未硬化的覆蓋部19A係各被聚合硬化，形成核心部11，又12，13及14，以及覆蓋部19(圖7~圖9，參照光波導10。圖7係例示光波導10之平面圖，圖8係沿著圖7之A-A線的剖面圖，圖9係沿著圖7之B-B線的剖面圖)。尚且，核心部11~14係各於核心部11~14之內部，未產生界面而連續性地一體地形成，而覆蓋部19係於覆蓋部19之內部未產生界面而一體地形成。 　　[0026] 尚且，在本形態中，準備支持體91而製造光波導，但支持體91係未必為必需之構成。例如，於形成在積體電路內或印刷基板內之凹狀的形狀內，製作未硬化的覆蓋部19A亦可，將該基板內的溝或槽隙作為支持體的代替而製作亦可。 　　另外，在本形態中，吐出部94則顯示1系統之例，但對於如此之形態係未限定，而自複數的吐出部94，同時吐出核心形成材料，同時地形成複數之未硬化的核心部(例如，11A~14A)亦可。 　　[0027] ＜覆蓋形成材料及核心形成材料＞ 　　在上述之製造方法中，形成覆蓋部之覆蓋形成材料，以及形成核心部之核心形成材料係如前述，只要在前述第2工程的溫度中對於未硬化的覆蓋部之黏度，換言之，形成未硬化之覆蓋部的覆蓋形成材料之黏度而言，形成前述未硬化之核心部的核心形成材料的黏度比則位於特定的範圍內，可適宜選擇採用以往的可使用於光波導之覆蓋部及核心部的形成之各種材料者。 　　具體而言，覆蓋形成材料係成為較以核心形成材料所形成之核心部的中心部為低折射率之材料，另外，覆蓋形成材料及核心形成材料之任一，均為藉由在前述第4工程之光照射或加熱處理而硬化之材料，例如，可適宜選擇而使用將聚矽氧樹脂，丙烯酸樹脂，乙烯樹脂，環氧樹脂，聚醯亞胺樹脂，聚烯烴樹脂，聚降冰片烯樹脂等作為主成分之材料等。另外，於覆蓋形成材料係例如，使碳黑等的吸收光之素材含有亦可。 　　[0028] 在本發明之製造方法中，可將組合特定構造之反應性聚矽氧化合物，和具有烯烴基及/或(甲基)丙烯醯基之化合物的聚合性組合物，作為光波導之覆蓋形成材料及/或核心形成材料而最佳地使用。 　　更詳細地說係例如，可將記載於國際公開2012/097836號小冊子之聚合性組成物，藉由折射率或黏度而作為覆蓋形成材料或核心形成材料而選擇。 　　[0029] 在本發明使用之上述覆蓋形成材料及上述核心形成材料係在藉由本發明之製造方法所成的光波導之形成中，具有於作業性優越之黏度而為佳。 　　例如，上述覆蓋形成材料的黏度係在25℃為500~ 20,000mPa･s，而上述核心形成材料係同為600~120,000 mPa･s而為佳。 　　尚且，如前述，在本發明之製造方法中，由於要求在前述第2工程的溫度中，對於未硬化之覆蓋部的黏度而言，形成前述未硬化的核心部之材料的黏度比係位於特定的範圍(1.20~6)內之情況，故呈形成覆蓋部(及核心部)之覆蓋形成材料，及形成核心部之核心形成材料的黏度，均滿足上述之黏度比地分別進行選擇即可。 [實施例] 　　[0030] 以下，舉出實施例，更具體地說明本發明，但本發明係不限定於下述之實施例者。 　　尚且，在實施例中，使用於試料的調製及物性的分析之裝置及條件係如以下。 　　[0031] (1) 攪拌脫泡機 　　裝置：(股)THINKY製 自轉･公轉攪拌機 THINKY MIXER(註冊商標)ARE-310 (2)¹ H NMR 　　裝置：Burker公司製 AVANCE III HD 　　測定頻率數：500MHz 　　測定溶媒：CDCl₃ 基準物質：四甲基矽烷(0.00ppm) (3) 膠體滲透層析儀(GPC) 　　裝置：(股)島津製作所製 Prominence(註冊商標)GPC系統 　　管柱：昭和電工(股)製 Shodex(註冊商標)GPC KF-804L及GPC KF-803L 　　管柱溫度：40℃ 　　溶媒：四氫呋喃 　　檢出器：RI 　　檢量線：標準聚苯乙烯 (4) 黏度 　　裝置：Anton Paar公司製 MCR流變計 MCR302 　　測定系統：錐板(直徑25mm、角度2度) 　　溫度：25℃ 　　旋轉數：1rpm 　　待機時間：5分鐘 (5) 數位顯微鏡 　　裝置：(股)KEYENCE製 VHX-5000系列 　　[0032] 另外，略記號係表示以下的意思。 　　DPSD：二苯基矽二醇[東京化成工業(股)製] 　　STMS：三甲氧基(4-乙烯基苯基)矽烷[信越化學工業(股)製] 　　DOG：二氧雜環乙二醇二丙烯酸酯[新中村化學工業(股)製 NK酯A-DOG] 　　DVB：二乙烯苯[新日鐵住金化學(股)製 DVB-810、純度81%] 　　I127：2-羥基-1-(4-(4-(2-羥基-2-甲基丙醯基)苯甲基)苯基)-2-甲基丙烷-1-酮[BASF JAPAN(股)製 IRGACURE (註冊商標)127] 　　TPO：二苯基(2,4,6-三甲基苯甲醯基)氧化膦[BASF JAPAN(股)製 IRGACURE(註冊商標)TPO] 　　[0033] [製造例1]反應性聚矽氧化合物(SC1)之製造 　　於具備凝縮器之1L的茄子型燒瓶，裝填DPSD 177g (0.80mol)、STMS 179g(0.80mol)、及甲苯141g，使用氮氣球，以氮而取代燒瓶中的空氣。將此反應混合物加熱至50℃後，添加氫氧化鋇水合物[Aldrich公司製]0.303g (1.6mmol)，更且以50℃進行2日攪拌進行脫醇縮合。將反應混合物冷卻至室溫(約23℃)，使用孔徑0.2μm之薄膜過濾器而除去不溶物。藉由使用減壓濃縮裝置，自此反應混合物，以50℃減壓餾去甲苯及副生成物的甲醇者，得到無色透明油狀物的反應性聚矽氧化合物(SC1)305g。 　　將所得到之反應性聚矽氧化合物之¹ H NMR頻譜，示於圖10。另外，藉由GPC所致之以聚苯乙烯換算所測定之重量平均分子量Mw係為1,300、而分散度Mw/Mn係為1.2。 　　[0034] [製造例2]反應性聚矽氧化合物(SC2)之製造 　　於具備凝縮器及丁斯塔克裝置之200L的茄子型燒瓶，裝填DPSD 43.3g(0.20mol)、STMS 44.9g(0.20mol)、及甲苯35g，使用氮氣球，以氮而取代燒瓶中的空氣。將此反應混合物加熱至50℃後，添加氫氧化鋇水合物[Aldrich公司製]38mg(0.2mmol)，以50℃進行1小時攪拌。更且，加熱至85℃後，將副生的甲醇除去於系統外同時，進行5小時攪拌而進行脫醇縮合。將反應混合物冷卻至室溫(約23℃)，使用孔徑0.2μm之薄膜過濾器而除去不溶物。藉由使用減壓濃縮裝置，自此反應混合物，以50℃減壓餾去甲苯者，得到無色透明油狀物的反應性聚矽氧化合物(SC2) 74.9g。 　　將所得到之反應性聚矽氧化合物之¹ H NMR頻譜，示於圖11。另外，藉由GPC所致之以聚苯乙烯換算所測定之重量平均分子量Mw係為1,600、而分散度：Mw(重量平均分子量)/Mn(數平均分子量)係為1.2。 　　[0035] [製造例3]硬化性組成物1之調製 　　在製造例1所製造之SC1 98.6質量份、DVB 1.4質量份、及TPO 1質量份，以50℃進行3小時攪拌混合。更且藉由進行2分鐘攪拌脫泡者，調製硬化性組成物1。 　　所得到之組成物的在25℃之黏度係為51,300mPa･s。 　　[0036] [製造例4~6]硬化性組成物2~4之調製 　　與製造例3同樣地進行，各調製表1所記載之硬化性組成物2~4。將所得到之各組成物的在25℃之黏度，合併顯示於表1。 　　[0037][0038] [實施例1] GI型光波導之製作 　　由表2所記載之條件，製作形成1通道的核心部於覆蓋部內之光波導。於以下具體地說明(參照圖1~圖5)。 　　[0039] 於縱15cm×橫3cm×厚度3mm之玻璃基板上(圖1：底板92)，貼上於中央具有縱10cm×橫1cm之開口部(圖1：開口部93a)的厚度500μm之聚矽氧橡膠薄片(圖1：外框93)，於其開口部，作為覆蓋材料而充填硬化性組成物2。此時，藉由對於水平方向傾斜約45度，更且使其靜置30分鐘者，均一地充填覆蓋材料於開口部，作成未硬化之覆蓋部(圖2：未硬化之覆蓋部19A)。 　　將充填此覆蓋材料之玻璃板，安裝於桌上型塗佈機器手臂[musashi-engineering(股)製 SHOTMASTER(註冊商標)300DS-S]之工作台。另外，於5mL UV區塊注射器[musashi-engineering(股)製 PSY-5EU-OR](圖3：吐出部94)中，作為核心材料而充填硬化性組成物1而進行脫泡，在對注射器吐出部(圖3：吐出部主體95)連接內徑150μm之金屬注射針[musashi-engineering(股)製 SN-30G-LF](圖3：針狀部96)之後，安裝於桌上型塗佈機器手臂。 　　接著，呈自玻璃基板上面至金屬注射針前端為止之高度(圖3：H₁ )則成為270μm地調整吐出部的位置。之後，將分配器[musashi-engineering(股)製 ML-808GXcom]的吐出壓力設定為550kPa，將桌上型塗佈機器手臂之描線動作速度(吐出部的移動速度)設定為14mm/秒。藉由使桌上型塗佈機器手臂的吐出程式動作之時，在自玻璃基板上面至金屬注射針前端為之高度為270μm之位置，呈光波導之長度則成為9.5cm地，將核心材料之硬化性組成物1，吐出至覆蓋材料之硬化性組成物2中，而形成未硬化的核心部(圖4：未硬化之核心部11A)之後，自未硬化之核心部拔去金屬注射針(圖5)。核心部描線結束後，立即將設置於桌上型塗佈機器手臂之連接於UV光源[200W水銀氙氣燈、HOYA CANDEO OPTRONICS(股)製 EXECURE 4000-D]的光纖光波導前端，以20mm/秒的速度進行3次掃描，再以照度1,000mW/cm² (365nm檢出)進行UV照射，使未硬化之核心部及未硬化之覆蓋部硬化而作成核心部及覆蓋部。尚且，上述作業係以室溫(約25℃)實施。 　　之後，使用刮刀而自玻璃基板剝離聚矽氧橡膠薄片之後，以150℃之烘箱進行20分鐘加熱。使用刮刀而使光波導的剖面露出，以光纖用砂紙研磨端面者，藉此得到長度5cm之GI型光波導。 　　[0040] 將所製作之光波導，垂直方向地設置於數位顯微鏡之平台，自下部的白色光源打光而以透過模式觀察光波導之剖面形狀。將結果示於圖12。另外，依據以下的基準而評估其形狀。將結果示於表2。 [剖面形狀] 　　A：略圓形 　　C1：橫長形且於上部為凹 　　C2：縱長形且於上部為凸 [縱橫比] 　　以畫像處理軟體[美國國立衛生研究所ImageJ]而解析剖面照片，計測核心部的最大寬度，及最大高度(於上部為凹形狀的情況係至凹部之最下部為止之高度)。將對於所得到之最大寬度及最大高度之任一為大之值而言之另一方的值的比，作為縱橫比而算出。尚且，核心部與覆蓋部之邊界係作為和包含各線分之直線上的畫素之最大亮度與最小亮度之平均值((最大亮度+最小亮度)/2)均等之亮度的點。 　　[0041] [實施例2~3，比較例1~2] 　　除變更為表2記載之材料、條件以外係與實施例1同樣地進行操作，製作光波導，觀察其剖面形狀而進行評估。將其結果，合併顯示於圖13~圖16，以及表2。 　　[0042][0043] 如圖12~圖14所示，對於覆蓋材料(未硬化的覆蓋部)之黏度而言的核心材料(形成未硬化之核心部的材料)之黏度比為1.2~5.7之實施例1~3的光波導係顯示此等之核心的剖面形狀則均接近於直徑50μm左右(實施例1及實施例2)或者30μm左右(實施例3)之正圓形狀的略圓形。 　　另一方面，在上述的黏度比則成為超過特定範圍(1~6)之13.5的比較例1之光波導中，顯示有核心的剖面為橫長形且於上部為凹之形狀(圖15)。 　　另外，在上述的黏度比則成為小於特定範圍之0.52的比較例2之光波導中，顯示有核心的剖面為縱長形且於上部為凸之形狀(圖16)。 　　[0044] 如以上，藉由本發明之光波導之製造方法，藉由將核心的形成材料與覆蓋的形成材料之黏度比作為特定的範圍之時，可得到核心的剖面形狀則更接近於正圓之略圓形之光波導。[0011] <Manufacturing method of optical waveguide> The manufacturing method of the optical waveguide of the present invention includes a first process of piercing the needle-like portion at the tip of the discharge portion into an unhardened covering portion, and discharging unhardened from the needle-like portion. At the same time as moving the needle-shaped portion into the uncured covering portion, forming a second process of covering the uncured core portion surrounding the uncured covering portion, and removing the uncured covering portion from the uncured covering portion. The third process of the needle-shaped portion and the fourth process of hardening the uncured covering portion and the uncured core portion. In addition, in the manufacturing method of the present invention, the first process, the second process, and the third process are repeatedly performed as a series of processes between the third process and the fourth process, and the uncured state is formed. After the covering part covers the surrounding unhardened core part, the fourth process of hardening the unhardened covering part and the aforementioned unhardened core part may be performed. [0012] In the method for manufacturing an optical waveguide of the present invention, as described later, it is characterized in that, at the temperature of the second process, the viscosity of the uncured cover part forms the material of the uncured core part. The viscosity ratio is 1.20 ~ 6. In addition, the second engineering system can usually be carried out at room temperature, and the viscosity of the non-hardened covering portion and the core portion is called, for example, a viscosity of 25 ° C. ± 5 ° C. Ideally, the viscosity ratio is 1.5-6, and more preferably 1.5-4. By setting the viscosity ratio to a range of 1.20 to 6, a GI-type optical waveguide capable of forming a core with a slightly circular cross-sectional shape can be formed, and further, the GI-type optical waveguide can be connected to suppress deterioration of insertion loss. Moreover, in the present invention, "slightly circular" means: the aspect ratio calculated from the maximum width (horizontal direction) and the maximum height (vertical direction) of the cross-sectional shape of the core (for any of the maximum width and the maximum height is The ratio of the larger value to the other value, that is, the maximum value for a perfect circle 1) is a shape of 0.8 or more. In particular, an aspect ratio of, for example, 0.9 or more is preferable as an optical waveguide that can further suppress deterioration of insertion loss. [0013] Hereinafter, an example of a practical series of steps for manufacturing the optical waveguide of the present invention will be described in detail. 1 to 6 are diagrams illustrating a part of a manufacturing process of an optical waveguide, and this manufacturing process may be referred to as an injection method. [0014] First, in the process shown in FIG. 1, a support body 91 is prepared. The support body 91 is a member provided on the peripheral edge portion of the bottom plate 92 having a substantially rectangular planar shape, and the outer frame 93 having the opening portion 93a having a substantially frame edge shape in a planar shape can be detachably mounted. As the material of each of the bottom plate 92 and the outer frame 93, for example, resin (acrylic acid), glass, silicon, ceramic, metal, or the like can be used. However, the bottom plate 92 and the outer frame 93 may not use the same material. It is preferable that the upper surface of the bottom plate 92 has a high flatness. [0015] Next, in the process shown in FIG. 2, a specific material is coated on the bottom plate 92 exposed in the frame 93 outside the support 91, and similarly expanded to produce a non-hardened layer with a certain thickness. Covering part 19A. The uncured covering portion 19A is coated with a covering forming material described later using, for example, a coating device (dispenser, etc.), a printing device, or the like, or can be produced by filling (injecting) from the opening portion 93a. The material (cover-forming material) of the uncured cover portion 19A may contain a light-absorbing material such as carbon black. The viscosity of the non-hardened cover portion 19A is not particularly limited, and the viscosity of the non-hardened core portion described later with respect to the viscosity may be adjusted to 1.20 to 6. In addition, the thickness of the non-hardened cover portion 19A can be arbitrarily determined by the diameter of the core portions 11 to 14 described later, manufacturing conditions, and the like, but it is preferably about several mm, and more preferably about 50 to 1,000 μm. . [0016] Next, in the process shown in FIG. 3, a coating device (not shown) having a discharge portion 94 (having a discharge portion main body 95 and a needle portion 96) is prepared, and the prepared coating device (not shown) (Shown in the figure), a part of the needle-like portion 96 at the tip of the ejection portion 94 is inserted into the uncured cover portion 19A (first process). The height H ₁ from the upper surface of the bottom plate 92 of the support body 91 to the front end of the needle-like portion 96 can be appropriately selected, but it can be, for example, about 100 to 1,000 μm (the thickness of the non-hardened cover portion 19A is several mm). Situation). [0017] In addition, the coating device (not shown) includes a CPU, a memory, and the like, and when the program is organized, the ejection section 94 has a specific movement speed and accuracy for the uncured cover section 19A. Good movement in X, Y, and Z directions. In addition, the needle-like portion 96 has, for example, a circular shape in cross section, and the coating device (not shown) has a function of ejecting a specific material from the inside of the ring of the needle-shaped portion 96 under a specific discharge pressure. . The inner diameter of the ring of the needle-like portion 96 can be appropriately selected, but it can be, for example, about 100 to 200 μm. The cross-sectional shape of the needle-like portion 96 may be a rectangular shape in addition to the circular shape. The coating device (not shown) is configured by, for example, a desktop coating robot arm or a dispenser. [0018] Next, in the process shown in FIG. 4, the coating device (not shown) is operated, and the needle-like portion 96 of the uncured cover portion 19A is self-punctured as a material for forming the uncured core portion. While ejecting a core-forming material described later, the needle-shaped portion 96 is moved into the uncured cover portion 19A to form an uncured core portion 11A (second process). Moreover, in FIG. 4, (A) is a plan view, and (B) is a cross-sectional view taken along line CC of (A). However, in (A), the illustration of the discharge portion 94 is omitted. The moving direction of the needle-like portion 96 can be selected as appropriate, but it is only moved in the X direction as an example here. The moving speed of the needle-like portion 96 can be appropriately selected, but it can be, for example, about 5 to 30 mm / s. The discharge pressure of the needle-like portion 96 can be appropriately selected, but it can be, for example, about 10 to 1,000 kPa. The viscosity of the non-hardened core portion 11A may be selected from the ratio of the viscosity of the non-hardened cover portion 19A to 1.20 to 6. [0019] By the moving speed of the discharge portion 94 or the discharge pressure of the needle-like portion 96, the inner diameter of the ring of the needle-like portion 96 is respectively matched with the material (core-forming material) forming the unhardened core portion 11A or When adjusting the properties (viscosity, etc.) of the material (cover-forming material) forming the non-hardened cover portion 19A, it is possible to connect the shape of the cross-section of the non-hardened core portion A to a slightly circular shape closer to a perfect circle. In addition, after hardening described later, the core portion 11 having a higher refractive index at the center portion and a lower refractive index nearer the peripheral portion can be formed. The diameter of the case where the cross-sectional shape of the non-hardened core portion 11A is slightly circular is, for example, about 5 to 200 μm. In addition, when the core forming material is discharged, the moving speed of the discharge portion 94 or the discharge pressure of the needle-like portion 96 is changed by a program or the like, thereby forming core portions 11 having different calibers (point size conversion). . [0020] Furthermore, the material (core forming material) of the non-hardened core portion 11A or the material (cover formation of the non-hardened cover portion 19A) is matched with the moving speed of the discharge portion 94 or the discharge pressure of the needle portion 96. When adjusting the properties (viscosity, etc.) of the material), a non-hardened core portion 11A having a slightly circular (cross-sectional shape) inner diameter which is smaller than the inner diameter of the ring of the needle-like portion 96 can also be produced. This is to adjust the viscosity of each material, and the more viscous non-hardened core 11A material is ejected from the needle-like portion 96. The friction between the inner side of the ring of the needle-like portion and the material becomes larger. Thus, the material is not easily ejected from the vicinity of the inner side surface of the ring, and the material is preferentially ejected only near the center portion of the ring without causing friction with the inner surface of the ring. In addition, the engineering system of FIG. 4 can usually be carried out at room temperature, but the temperature can be adjusted by a temperature adjustment device (not shown) such as a cooling plate. In particular, in the case where a core portion 11A having a fine diameter of 10 μm or less is produced, for example, it is preferably 10 to 20 ° C. [0021] In the process shown in FIG. 4, it is shown that a support 91 having an unhardened cover portion 19A is fixed, and a needle-like portion 96 is moved within the unhardened cover portion 19A to form an unhardened core portion 11A. example. However, the shape is not limited to this. For example, the needle-shaped portion 96 may be fixed, and the support 91 having the uncured cover portion 19A may be moved to form the uncured core portion 11A. [0022] Next, in the process shown in FIG. 5, the ejection portion 94 is moved in the Z direction from the state shown in FIG. 4, and the needle-like portion 96 is pulled out from the uncured cover portion 19A (third process). Moreover, after that, the penetration of the uncured covering portion 19A of the needle portion 96 of the process of FIG. 3 and the process of forming the uncured core portion 11A of FIG. 4 and the uncured covering of the process of FIG. 5 are repeatedly performed. The needle-shaped portion 96 of the portion 19A is pulled out, and as shown in FIG. 6, the unhardened core portions 12A, 13A, and 14A may be formed in parallel to the unhardened core portion 11A. For the unhardened core portions 12A, 13A, and 14A, the same type of core forming material as the unhardened core portion 11A may be used, and different types of core forming materials may be used. When a plurality of core portions are formed, the distance between adjacent core portions may be, for example, about 20 to 300 μm. As described above, the uncured covering portion 19A has a moderate fluidity (viscosity). Even if the needle-shaped portion 96 is pulled out from the uncured covering portion 19A, the removed traces are not left. In addition, After the hardened core portions 11A, 12A, 13A, and 14A, no interface is formed with the unhardened cover portion 19A. In addition, in FIGS. 5 and 6, (A) is a plan view, and (B) is a cross-sectional view taken along a CC line (FIG. 5) or a DD line (FIG. 6) of (A). However, in (A) of each figure, the illustration of the discharge part 94 is abbreviate | omitted. [0023] After the processes shown in FIGS. 5 and 6 (not shown), the unhardened core portions 11A, 12A, 13A, and 14A, and the unhardened cover portion 19A are subjected to a specific method described later, that is, , Harden by irradiating light (ultraviolet rays, etc.) or heat treatment to harden it (process 4). In the case of using a material that is not completely hardened only by irradiation of light, heating may be performed after the irradiation of light. [0024] In the case of the photo-hardening, examples of the active light used for light irradiation include ultraviolet rays, electron rays, X-rays, and the like. As a light source used for ultraviolet irradiation, solar rays, chemical lamps, low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, xenon lamps, UV-LEDs, etc. can be used. In addition, when post-baking according to necessity after light irradiation, specifically, using a hot plate, an oven, etc., usually, it can be hardened (polymerized) by heating at 50 to 300 ° C for 1 to 120 minutes. ) Finisher. The above-mentioned case of thermal curing is not particularly limited as a heating condition, and usually, it can be appropriately selected from a range of 50 to 300 ° C and 1 to 120 minutes. The heating means is not particularly limited, but examples thereof include a hot plate and an oven. [0025] Through this hardening process, the unhardened core portions 11A, 12A, 13A, and 14A, and the unhardened cover portion 19A are each polymerized and hardened to form the core portions 11, 12 and 13 and 14, and Covering portion 19 (FIGS. 7 to 9 with reference to the optical waveguide 10. FIG. 7 is a plan view illustrating the optical waveguide 10, FIG. 8 is a cross-sectional view taken along line AA of FIG. 7, and FIG. 9 is taken along line BB of FIG. 7 Sectional view). In addition, the core portions 11 to 14 are each formed integrally and continuously in the core portions 11 to 14 without an interface, and the cover portion 19 is integrally formed without an interface in the cover portion 19. [0026] Furthermore, in this embodiment, the support 91 is prepared to manufacture an optical waveguide, but the support 91 is not necessarily a necessary configuration. For example, an unhardened cover portion 19A may be produced in a concave shape formed in a integrated circuit or a printed circuit board, or a groove or a gap in the circuit board may be produced instead of a support. In addition, in this embodiment, the ejection portion 94 shows an example of one system, but there is no limitation to such a configuration, and the plural ejection portions 94 simultaneously eject the core-forming material and simultaneously form a plurality of unhardened core portions. (For example, 11A to 14A). [0027] <Cover Forming Material and Core Forming Material> In the manufacturing method described above, the cover forming material forming the covering portion and the core forming material forming the core portion are as described above, as long as the temperature is not higher than the temperature of the second process described above. The viscosity of the hardened cover, in other words, the viscosity of the cover-forming material forming the non-hardened cover, the viscosity ratio of the core-forming material forming the aforementioned non-hardened core is within a specific range, and the past can be appropriately selected and used. Various materials that can be used for the formation of the covering part and the core part of the optical waveguide. Specifically, the cover-forming material is a material having a lower refractive index than the center portion of the core portion formed by the core-forming material. In addition, any of the cover-forming material and the core-forming material is obtained in the fourth step. Materials that are hardened by light irradiation or heat treatment of engineering. For example, silicone resin, acrylic resin, vinyl resin, epoxy resin, polyimide resin, polyolefin resin, and polynorbornene resin can be appropriately selected and used. And other materials as the main component. In addition, the cover forming material may contain, for example, a light absorbing material such as carbon black. [0028] In the manufacturing method of the present invention, a polymerizable composition combining a reactive polysiloxane having a specific structure and a compound having an olefin group and / or a (meth) acryl group can be used as the optical waveguide. The cover forming material and / or the core forming material are optimally used. More specifically, for example, the polymerizable composition described in International Publication No. 2012/097836 can be selected as a cover-forming material or a core-forming material by a refractive index or a viscosity. [0029] The cover-forming material and the core-forming material used in the present invention preferably have a viscosity excellent in workability in the formation of the optical waveguide formed by the manufacturing method of the present invention. For example, the viscosity of the cover forming material is preferably 500 to 20,000 mPa ･ s at 25 ° C, and the core forming material is preferably 600 to 120,000 mPa ･ s. Moreover, as mentioned above, in the manufacturing method of the present invention, it is required that the viscosity ratio of the material forming the non-hardened core portion be at a specific temperature for the viscosity of the unhardened cover portion at the temperature of the second process. In the range (1.20 ~ 6), the covering forming materials forming the covering portion (and the core portion) and the viscosity of the core forming material forming the core portion can be selected separately so as to satisfy the above-mentioned viscosity ratio. [Examples] [0030] Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples. In the examples, the devices and conditions used for the preparation of the samples and the analysis of the physical properties are as follows. (1) Stirring and defoaming device: (share) THINKY MIXER (registered trademark) ARE-310 (2) ¹ H NMR device: AVANCE III HD manufactured by Burker company Measurement frequency: 500MHz Solvent: CDCl ₃ Reference material: Tetramethylsilane (0.00ppm) (3) Colloidal permeation chromatography (GPC) Device: (Stock) Shimadzu Corporation Prominence (registered trademark) GPC system column: Showa Denko Corporation Shodex (registered trademark) GPC KF-804L and GPC KF-803L Column temperature: 40 ° C Solvent: Tetrahydrofuran Detector: RI Calibration line: Standard polystyrene (4) Viscosity device: MCR rheometer manufactured by Anton Paar MCR302 measuring system: cone plate (25mm diameter, 2 degrees) Temperature: 25 ° C Rotation number: 1rpm Standby time: 5 minutes (5) Digital microscope device: (share) Keyence VHX-5000 series [0032] In addition, abbreviated The meaning is as follows. DPSD: Diphenyl silicon glycol [manufactured by Tokyo Chemical Industry Co., Ltd.] STMS: trimethoxy (4-vinylphenyl) silane [manufactured by Shin-Etsu Chemical Industry Co., Ltd.] DOG: dioxane glycol di Acrylate [NK ester A-DOG manufactured by Shin Nakamura Chemical Industry Co., Ltd.] DVB: Divinylbenzene [DVB-810 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., purity 81%] I127: 2-hydroxy-1- (4 -(4- (2-hydroxy-2-methylpropanyl) benzyl) phenyl) -2-methylpropane-1-one [IRGACURE (registered trademark) made by BASF JAPAN (Stock) 127] TPO: Diphenyl (2,4,6-trimethylbenzylidene) phosphine oxide [IRGACURE (registered trademark) TPO manufactured by BASF JAPAN] [0033] [Production Example 1] Reactive polysiloxane (SC1 ) Was manufactured in a 1L eggplant-type flask equipped with a condenser, filled with 177 g (0.80 mol) of DPSD, 179 g (0.80 mol) of STMS, and 141 g of toluene, and replaced the air in the flask with nitrogen using a nitrogen balloon. After heating this reaction mixture to 50 ° C, 0.303 g (1.6 mmol) of barium hydroxide hydrate [manufactured by Aldrich Co., Ltd.] was added, and dealcoholization condensation was performed by stirring at 50 ° C for 2 days. The reaction mixture was cooled to room temperature (about 23 ° C), and insoluble matter was removed using a membrane filter having a pore size of 0.2 µm. By using a reduced-pressure concentration device, from this reaction mixture, toluene and by-product methanol were distilled off under reduced pressure at 50 ° C. to obtain 305 g of a reactive polysiloxane (SC1) as a colorless transparent oily substance. The ¹ H NMR spectrum of the obtained reactive polysiloxane is shown in FIG. 10. In addition, the weight average molecular weight Mw measured by GPC in terms of polystyrene was 1,300, and the degree of dispersion Mw / Mn was 1.2. [Production Example 2] Reactive polysiloxane (SC2) was produced in a 200L eggplant-type flask equipped with a condenser and a Ding Stark device, and filled with DPSD 43.3 g (0.20 mol) and STMS 44.9 g (0.20 mol) and 35 g of toluene, using a nitrogen balloon to replace the air in the flask with nitrogen. After heating this reaction mixture to 50 degreeC, 38 mg (0.2 mmol) of barium hydroxide hydrate [made by Aldrich company] were added, and it stirred at 50 degreeC for 1 hour. Further, after heating to 85 ° C., the byproduct methanol was removed from the system, and stirring was performed for 5 hours to perform dealcoholization condensation. The reaction mixture was cooled to room temperature (about 23 ° C), and insoluble matter was removed using a membrane filter having a pore size of 0.2 µm. By using a reduced-pressure concentration device, from this reaction mixture, toluene was distilled off under reduced pressure at 50 ° C to obtain 74.9 g of a reactive polysiloxane (SC2) as a colorless transparent oily substance. The ¹ H NMR spectrum of the obtained reactive polysiloxane is shown in FIG. 11. In addition, the weight average molecular weight Mw measured by GPC in terms of polystyrene was 1,600, and the degree of dispersion: Mw (weight average molecular weight) / Mn (number average molecular weight) was 1.2. [Production Example 3] Preparation of hardenable composition 1 98.6 parts by mass of SC1, 1.4 parts by mass of DVB, and 1 part by mass of TPO produced in Production Example 1 were stirred and mixed at 50 ° C for 3 hours. Furthermore, the hardening composition 1 was prepared by stirring and defoaming for 2 minutes. The viscosity of the obtained composition at 25 ° C was 51,300 mPa ･ s. [Production Examples 4 to 6] The hardening compositions 2 to 4 were prepared in the same manner as in Production Example 3. Each of the hardening compositions 2 to 4 described in Table 1 was prepared. The viscosity of each obtained composition at 25 ° C is shown in Table 1. [0037] [Example 1] GI-type optical waveguide was manufactured According to the conditions described in Table 2, an optical waveguide in which the core portion of the 1-channel was formed in the covering portion was fabricated. This will be specifically described below (see FIGS. 1 to 5). [0039] On a glass substrate having a length of 15 cm × 3 cm × thickness 3 mm (FIG. 1: base plate 92), a 500 μm thick aggregate having an opening portion (FIG. 1: opening portion 93 a) having a length of 10 cm × 1 cm in the center is pasted. The silicone rubber sheet (FIG. 1: Outer frame 93) is filled with the curable composition 2 as a covering material in the opening portion. At this time, by tilting the horizontal direction by about 45 degrees and letting it stand for 30 minutes, the opening material is uniformly filled in the opening portion to form an unhardened cover portion (FIG. 2: Unhardened cover portion 19A). The glass plate filled with this covering material was mounted on a table of a desktop coating robotic arm [SHOTMASTER (registered trademark) 300DS-S] made by a musashi-engineering company. In addition, a 5 mL UV block syringe [PSY-5EU-OR manufactured by Musashi-Engineering Co., Ltd.] (Fig. 3: Discharge section 94) was filled with the hardening composition 1 as a core material to defoam, and the syringe was The ejection part (Fig. 3: ejection part main body 95) is connected to a metal injection needle [musashi-engineering (strand) SN-30G-LF] (Fig. 3: needle part 96) with an inner diameter of 150 μm, and then it is mounted on a table top Cloth robot arm. Next, the height from the upper surface of the glass substrate to the tip of the metal injection needle (FIG. 3: H ₁ ) was adjusted to the position of the ejection portion at 270 μm. Thereafter, the discharge pressure of the dispenser [musashi-engineering (ML-808GXcom)] was set to 550 kPa, and the line drawing operation speed (moving speed of the discharge portion) of the desktop coating robot arm was set to 14 mm / sec. When the ejection program of the desktop coating robot arm is operated, the height from the top of the glass substrate to the front end of the metal injection needle is 270 μm, and the length of the optical waveguide becomes 9.5 cm. The hardening composition 1 is discharged into the hardening composition 2 of the covering material to form an unhardened core portion (FIG. 4: the unhardened core portion 11A), and then the metal injection needle is removed from the unhardened core portion ( Figure 5). Immediately after the drawing of the core part, the front end of the optical fiber waveguide connected to the UV light source [200W mercury xenon lamp, HOYA CANDEO OPTRONICS (EXCURE 4000-D)] installed on the desktop coating robot arm was set at 20 mm / sec. Scan three times at a high speed, and then perform UV irradiation at an illuminance of 1,000 mW / cm ² (detected at 365 nm) to harden the unhardened core portion and the unhardened cover portion to form the core portion and the cover portion. Moreover, the above-mentioned operation is performed at room temperature (about 25 ° C). After that, the silicone rubber sheet was peeled from the glass substrate using a doctor blade, and then heated in an oven at 150 ° C. for 20 minutes. Using a doctor blade to expose the cross section of the optical waveguide, and polishing the end surface with sandpaper for optical fibers, a GI optical waveguide having a length of 5 cm was obtained. [0040] The manufactured optical waveguide was set vertically on a platform of a digital microscope, and a white light source at the lower part was illuminated to observe the cross-sectional shape of the optical waveguide in a transmission mode. The results are shown in FIG. 12. The shape was evaluated based on the following criteria. The results are shown in Table 2. [Cross section shape] A: Slightly circular C1: Horizontally long and concave at the top C2: Vertically long and convex at the top [Aspect ratio] Analyze the cross-section photos with image processing software [National Institutes of Health ImageJ], Measure the maximum width and the maximum height of the core (the height from the bottom to the bottom of the recess when the top is concave). The ratio of the other value to one of the obtained maximum width and maximum height is calculated as the aspect ratio. In addition, the boundary between the core portion and the covering portion is a point of equal brightness to the average of the maximum brightness and the minimum brightness ((maximum brightness + minimum brightness) / 2) of the pixels on a straight line containing each line. [Examples 2 to 3, Comparative Examples 1 to 2] Except changing to the materials and conditions described in Table 2, the same operation as in Example 1 was performed to produce an optical waveguide, and the cross-sectional shape was evaluated. The results are combined and shown in FIG. 13 to FIG. 16 and Table 2. [0042] [0043] As shown in FIG. 12 to FIG. 14, the viscosity ratio of the core material (the material forming the unhardened core portion) with respect to the viscosity of the cover material (the uncured cover portion) is 1.2 to 5.7. The optical waveguide systems of ~ 3 show that the cross-sectional shapes of these cores are almost circular, which are close to the perfect circular shape with a diameter of about 50 μm (Example 1 and Example 2) or about 30 μm (Example 3). On the other hand, in the optical waveguide of Comparative Example 1 in which the above-mentioned viscosity ratio is 13.5 exceeding a specific range (1 to 6), the shape showing the cross section of the core is horizontally elongated and the shape is concave at the upper portion (Fig. 15) . In addition, in the optical waveguide of Comparative Example 2 in which the above-mentioned viscosity ratio was less than 0.52 in a specific range, the cross section showing the core was elongated and the shape was convex at the upper portion (FIG. 16). [0044] As described above, with the manufacturing method of the optical waveguide of the present invention, when the viscosity ratio of the core forming material and the covering forming material is set to a specific range, the cross-sectional shape of the core is closer to a perfect circle. A slightly circular optical waveguide.

[0045][0045]

10‧‧‧光波導10‧‧‧ Optical Waveguide

11、12、13、14‧‧‧核心部11, 12, 13, 14‧‧‧ Core

11A、12A、13A、14A‧‧‧未硬化之核心部11A, 12A, 13A, 14A‧‧‧Unhardened core

19‧‧‧覆蓋部19‧‧‧ Covering Department

19A‧‧‧未硬化的覆蓋部19A‧‧‧Uncured Cover

91‧‧‧支持體91‧‧‧ support

92‧‧‧底板92‧‧‧ floor

93‧‧‧外框93‧‧‧Frame

94‧‧‧吐出部94‧‧‧ Spit

95‧‧‧吐出部主體95‧‧‧ Main body of spit

96‧‧‧針狀部96‧‧‧ Needle

H₁‧‧‧高度H ₁ ‧‧‧ height

[0010] 　　圖1係例示光波導之製造工程的圖(其1)。 　　圖2係例示光波導之製造工程的圖(其2)。 　　圖3係例示光波導之製造工程的圖(其3)。 　　圖4係例示光波導之製造工程的圖(其4)。 　　圖5係例示光波導之製造工程的圖(其5)。 　　圖6係例示光波導之製造工程的圖(其6)。 　　圖7係例示光波導之製造工程的圖(其7：光波導10之平面圖)。 　　圖8係例示光波導之製造工程的圖(其8：沿著圖7之A-A線的剖面圖)。 　　圖9係例示光波導之製造工程的圖(其9：沿著圖7之B-B線的剖面圖)。 　　圖10係顯示在製造例1所得到之反應性聚矽氧化合物(SC1)之¹ H NMR頻譜的圖。 　　圖11係顯示在製造例2所得到之反應性聚矽氧化合物(SC2)之¹ H NMR頻譜的圖。 　　圖12係顯示在實施例1所製作之光波導的藉由數位顯微鏡之觀察結果(透過模式)的剖面照片。 　　圖13係顯示在實施例2所製作之光波導的藉由數位顯微鏡之觀察結果(透過模式)的剖面照片。 　　圖14係顯示在實施例3所製作之光波導的藉由數位顯微鏡之觀察結果(透過模式)的剖面照片。 　　圖15係顯示在比較例1所製作之光波導的藉由數位顯微鏡之觀察結果(透過模式)的剖面照片。 　　圖16係顯示在比較例2所製作之光波導的藉由數位顯微鏡之觀察結果(透過模式)的剖面照片。1 is a diagram (No. 1) illustrating a manufacturing process of an optical waveguide. FIG. 2 is a diagram (part 2) illustrating a manufacturing process of an optical waveguide. FIG. 3 is a diagram (part 3) illustrating a manufacturing process of an optical waveguide. FIG. 4 is a diagram (part 4) illustrating a manufacturing process of an optical waveguide. FIG. 5 is a diagram (part 5) illustrating a manufacturing process of the optical waveguide. FIG. 6 is a diagram (part 6) illustrating a manufacturing process of an optical waveguide. FIG. 7 is a diagram illustrating a manufacturing process of the optical waveguide (No. 7: a plan view of the optical waveguide 10). FIG. 8 is a diagram illustrating a manufacturing process of an optical waveguide (No. 8: a cross-sectional view taken along a line AA in FIG. 7). FIG. 9 is a diagram illustrating a manufacturing process of an optical waveguide (No. 9: a cross-sectional view taken along a line BB in FIG. 7). FIG. 10 is a diagram showing a ¹ H NMR spectrum of a reactive polysiloxane (SC1) obtained in Production Example 1. FIG. 11 is a view showing a ¹ H NMR spectrum of a reactive polysiloxane (SC2) obtained in Production Example 2. FIG. FIG. 12 is a cross-sectional photograph showing an optical waveguide observation result (transmission mode) of the optical waveguide prepared in Example 1. FIG. FIG. 13 is a cross-sectional photograph showing an optical waveguide observation result (transmission mode) of the optical waveguide prepared in Example 2. FIG. FIG. 14 is a cross-sectional photograph showing the observation result (transmission mode) by a digital microscope of the optical waveguide prepared in Example 3. FIG. FIG. 15 is a cross-sectional photograph showing an optical waveguide observation result (transmission mode) of the optical waveguide produced in Comparative Example 1. FIG. FIG. 16 is a cross-sectional photograph showing an optical waveguide observation result (transmission mode) of the optical waveguide produced in Comparative Example 2. FIG.

Claims (3)

一種光波導之製造方法係具有：刺入吐出部前端的針狀部於未硬化之覆蓋部的第1工程，和自前述針狀部吐出未硬化之材料的同時，使前述針狀部移動在前述未硬化之覆蓋部內，形成使前述未硬化之覆蓋部被覆周圍之未硬化的核心部之第2工程，和自前述未硬化之覆蓋部拔去前述針狀部之第3工程，和使前述未硬化之覆蓋部及前述未硬化之核心部硬化的第4工程之光波導之製造方法，其特徵為 　　在前述第2工程的溫度中，對於前述未硬化之覆蓋部的黏度而言，形成前述未硬化的核心部之材料的黏度比則為1.20~6者。An optical waveguide manufacturing method includes a first process of piercing a needle-shaped portion at the tip of a discharge portion into an unhardened covering portion, and simultaneously moving the needle-shaped portion to discharge the unhardened material from the needle-shaped portion. A second process of forming an uncured core portion covering the surroundings of the uncured covering portion in the uncured covering portion, a third process of removing the needle portion from the uncured covering portion, and forming the aforementioned The method for manufacturing an uncured covering part and the optical waveguide of the fourth process in which the uncured core part is cured is characterized in that at the temperature of the second process, the viscosity of the uncured covering part is formed as described above. The viscosity ratio of the unhardened core material is 1.20 ~ 6. 如申請專利範圍第1項記載之光波導之製造方法，其中，於前述第3工程與前述第4工程之間，作為一連串的工程而重複實施前述第1工程，前述第2工程及前述第3工程，形成使前述未硬化之覆蓋部被覆周圍之複數的未硬化之核心部。For example, the manufacturing method of the optical waveguide described in item 1 of the scope of the patent application, wherein the aforementioned first project, the aforementioned second project, and the aforementioned third project are repeatedly performed as a series of processes between the aforementioned third project and the aforementioned fourth project. Engineering to form a plurality of unhardened core portions that cover the surroundings of the unhardened covering portion. 如申請專利範圍第1項或第2項記載之光波導之製造方法，其中，前述光波導為在其剖面的核心部之折射率，則將核心部的中心作為最大值而朝向外周部，折射率則連續性地降低之光波導。For example, if the method of manufacturing an optical waveguide according to item 1 or 2 of the patent application scope is that the optical waveguide has a refractive index at the core portion of the cross section, the center of the core portion is taken as the maximum value, and is refracted toward the outer peripheral portion. The rate is continuously reduced in the optical waveguide.